Organotin-,arsenic and antimony 1,1-ethylene dithiolates



United States Patent 3,429,905 0RGANOTIN-, ARSENIC AND ANTIMONY1,1-ETHYLENE DITHIOLATES William Lindsay Mosby, North Plainfield, N.J.,assignor to American Cyanamid Company, Stamford, Conn., a

corporation of Maine No Drawing. Filed July 23, 1965, Ser. No. 474,476U.S. Cl. 260429.7 6 Claims Int. Cl. C07d 105/00, 105/06, 107/00 ABSTRACTOF THE DISCLOSURE Unsaturated dithiol compounds of the formula:

wherein M is a polyvalent metal selected from the group consisting ofantimony, arsenic and tin; R is a monovalent hydrocarb-yl radicalselected from the group consisting of lower alkyl, monocyclic andbicyclic aromatic, and monocyclic ar(lower alkyl); n is the valence ofM; A is a monovalent radical selected. from the group consisting of CN,COOR, CONH OONHR, CONR COR and N0 and A is a member selected from thegroup consisting of hydrogen and A. These compounds are prepared byreaction of the corresponding alkali metal 1,1- ethylenedithiolate witha metal dihalide inan inert medium, The compounds are useful asfungicides, herbicides and bacteriocides.

This invention relates to, and has as its object, the provision of newcompounds. More particularly, it relates to organo-metallic derivativesof unsaturated, carhon-containing dithiols represented by the Formula I:

s a' 1 wherein M is a polyvalent metal selected from the groupconsisting of antimony, arsenic and tin; R is a monovalent hydrocanbylradical selected from the group consisting of lower alkyl (includingcycloalkyl of 4-6 canbons), monoor bicyclic arom'atic (e.-g., phenyl andnaphthyl as well as lower alkyl substituted analogs), and monocyclicar(lower alkyl); n is the valance of M; A is a monovalent radicalselected from the group consisting of CN, COOR, CONH CONHR, CONR COR andN0 and A is a member selected from the group consisting of hydrogen andA.

The compounds of this invention exhibit biocidal properties. Thus, theyare bacteriocidal, inhibiting the growth of E. coli, Staph. aureus andB. mycoides; fungicidal, inhibiting growth of Aspen niger, Fusariummoniliform and Penicillium citrium; and herbicidal, killing wheat andradish seeds. Accordingly, they can be used agriculturally inconventional formulations as fungicides, herbicides and bacteriocides.

To prepare the compounds of this invention, an alkali metal1,1-ethylenedithiolate is reacted with a metal dihalide as in thefollowing equation:

3,429,905 Patented Feb. 25, 1969 wherein R, M, A, A and n are as definedabove, hal is halogen of atomic number above 9 and M is an alkali metalsuch as sodium or potassium. The reaction can be carried out bycontacting approximately equimolar amounts of the dihalide anddithiolate in a suitable reaction medium.

Suitable inert reaction media include ethylene glycol, diethyl ether,acetonitrile, dimethylformamide, Diglyme, dimethylacetamide,dimethylsulfoxide, etc.

When the two reactants are contacted, some heat is usually evolved.Therefore, it is usually advantageous to combine the reactants at roomtemperature. Under certain conditions, it may be necessry to provide acooling means to remove the heat of reaction. In a few cases, it may benecessary to apply heat to promote the completion of the reaction.Temperatures between room temperature and the boiling point of thereaction medium may be used The reactions are rapid and usually requireonly a short time for completion.

The reaction products may be isolated by any convenient means. It isadvantageous to add water, when a water-miscible reaction medium hasbeen used, Whereupon the product precipitates, if it is not alreadyprecipitated.

Suitable dithiolates are alkali metal derivatives of 1,1-ethylenedithiols such as l,1-dimercapto-2,Z-dicyanoethylene, 1,1dimercapto-Z,2-%bis(ethoxyoanbo)ethylene,1,1-di1mercapto-2-cyano-2-canbamoylethylene,1,1-dimercapto-2,2-diacetylethylene and 1,1-dimercapto-2-nitroethylene.

Five types of ongano-metall ic dihalides may be used in the preparationof the compounds of this invention. They are shown in the followinggeneral formulae:

hal R hal hal R hal R l RAs R A R-Sl R Sb /Sr hrl R hal hal B, 112.1 haIV V VI VII VIII Accordingly, five main types of compounds of Formula Ican be obtained by varying the particular dihalide which is reacted withthe dithiolate. The types are shown in the following formulae:

Representative organo dihalides of trivalent arsenic in Formula IV arealkyland aryl-dihaloarsines, such as methyldichloroarsine,methyldiiodoarsine, methyldichloroarsine, ethyldibromoarsine,amyldibromoarsine, heptyldichloroarsine, trifluoromethyldibromoarsine,ethoxyetheyldichloroarsine, phenyldibromoarsine, phenyldiiodoarsine,phenyldichloroarsine, o-tolyldichloroarsine, 2-naphthyldichloroarsine,p-chlorophenyldichloroarsine, rn-nitrophenyl dichloroarsine, 2,5dimethylphenyldichloroarsine, 4-acetamidophenyldichloroarsine,benzyldichloroarsine, etc.

Representative organo dihalides of pentavalent arsenic in Formula V aretrialkyland triaryl-diha'loarsenic compounds, such astrimethyldichloroarsenic, trimethyldibromoarsenic,triethyldiiodoarsenic, diethylphenyldichloroarsenic,diphenylethyldichloroarsenic, ethylphenyl-ptolyldichloroarsenic,triphenyldichloroarsenic, tri-p-tolyldichloroarsenic,tri-1-naphthyldichlor0arsenic, etc.

Representative organo dihalides of trivalent antimony in Formula VI arealkyland aryl-dihalostibines, such as methyldichlorostibine,ethyldichlorostibine, phenyldiiodostibine, p nitrophenyldichlorostibine,p tolyldichlorostibine, p-ethylphenyldichlorostibine,2-naphthyldichlorostibine, etc.

Representative organo dihalides of pentavalent antimony in Formula VIIare trialkyland triaryl-dihaloantimony compounds, such astrimethyldibromoantimony, trimethyldichloroantimony,triphenyldibromoantimony, triphenyldichloroantimony,triphenyldiiodoantimony, tris- (p-chlorophenyl)dichloroantimony,tri-2,4-xy1yldichloroantimony, tri-l-naphthyldibromoantimony, etc.

Representative organo-tin dihalides of Formula VIII are dialkylanddiaryl-dihalo-tin compounds such as dimethyldichlorotin,diethyldibromotin, dibutyldibromotin, diamyldichlorotin,dioctyldichlorotin, didecydichlorotin, butylpropyldichlo'rotin,diphenyldiiodotin, di p tolyldichlorotin, bis(pmethoxyphenyl)dichlorotin, dibenzyldiiodotin, dicyclohexyldichlorotin,etc.

The following examples in which parts and percentages are by weight, arepresented to further illustrate the present invention.

EXAMPLE 1 2,2-dibuty1-4-dicyanomethylene-1,3,2-dithiastannetane Amixture of 3.04 parts (0.01 mole) of dibutyldichlorotin and 2.18 parts(0.01 mole) of dipotassium dimercaptomethylenemalonitrile is trituratedat room temperature in about 10 parts of dimethylformamide. Water isadded and the precipitate is recrystallized from isopropanol. Theproduct melts at 253-254.5 C.

EXAMPLE 2 4-dicyanomethyllene-Z-phenyl-1,3,2-dithiarsetane water,methanol, and ligroin. The product melts at 176.5-

EXAMPLE 3 4-dicyanomethy1ene-2,2-diphenyl-1,3,2-dithiastannetane 4EXAMPLE 4 4-dicyanomethylene-2,2,2-triphenyl-1,3,2-dithiastibetane Amixture of 2.12 parts (0.005 mole) of triphenyldichloroantimony and 1.20parts (0.0055 mole) of dipotassium dimercaptomethylenemalonitrile inabout 5 parts of dimethylformamide is agitated with slight evolution ofheat. Water is gradually added. The precipitate is filtered, washed withwater, methanol and fiinally recrystallized from methanol. The productmelts at 1295- 13 1.5 C.

EXAMPLE 5 2,2-dibutyl-4-nitromethylene-1,3,2-dithiastannetane A mixtureof 3.04 parts (0.01 mole) of dibutyldichlorotin and 2.13 parts (0.01mole) of dipotassium 2- nitro-l,l-ethylenedithiol is triturated in abouttwo parts of dimethylformamide. Water is added, the precipitate isseparated by filtration, and washed with water, methyl alcohol and ethylacetate. The product melts at 122.5-

EXAMPLE 6 4-nitromethylene-2-pheny1-1,3,2-dithiarsetane CaHr-AS C=CHNO2A mixture of 2.13 parts (0.01 mole) of dipotassium2-nitro-1,1-ethylenedithiol and 4.06 parts (0.01 mole) ofphenyldichloroarsine is triturated in about 2 parts ofdimethylformamide. The reaction mixture is then poured into about 500parts of water. A gummy precipitate is triturated with water until itbecomes granular. The precipitate is recrystallized by dissolving inethyl acetate and pouring into ligroin. The product, after filtering,washing with ligroin and drying, melts at 131.5134.0 C.

EXAMPLE 7 2,2-diphenyl-4-nitromethylene-1,3,2-dithiastannetane Solutionsof 6.88 parts of diphenyldichlorotin in about 10 parts ofdimethylformamide and 4.29 parts of dipotassium2-nitro-1,l-ethylenedithiol in about 5 parts of dimethylformamide arecombined. The resulting solution is slowly added to about 1,500 parts ofwater containing a little salt. The yellow precipitate is separated byfiltration, washed with water and dried. The product, after trituratingwith benzene and washing with ligroin, melts at 151.5153.0 C.

EXAMPLE 8 4-dicyanomethylene-2,2,2-trimethyl-1,3,2-dithiarsetaneFollowing the procedure of Example 2, except for the use of an equlmolaramount of trimethyldibromoarsenic as the dihalide, the above product isobtained.

EXAMPLE 9 4-dicyanomethy1ene-2,2-dibenzy1-1,3,2-dithiastannetaneFollowing the procedure of Example 1, except for the use of an equimolaramount of dibenzyldibromotin as the dihalide, the above product isobtained.

EXAMPLE 10 4-dicyanomethylene-2-(2 naphthy1)-1,3 ,2-dithiastibetaneFollowing the procedure of Example 1, except for the use of an equimolaramount of Z-naphthyldichlorostibine as the dihalide, the above productis obtained.

EXAMPLE 11 4-bis(ethoxycarbo)methylene-2,2-diphenyl-1,3,2-dithiastannetane S CO 0 CzHs 4-( l-carbamoyl-l-cyanornethylene)-2-methyl-1,3, Z-dithiastibetane This product is obtained by reactingsodium 2-cyano- Z-carbamoyl-1,1-ethylenedithiolate withmethyldichlorostibine in the manner of Example 1.

6 EXAMPLE 13 4-diacetylmethylene-Z,2,2-triphenyl-1,3,2-dithiarsetane s 00 CH;

S COCH:

Following the procedure of Example 1, except for the use ofequimolecular amounts of triphenyldichloroarsenic and1,1-dimercapto-2,2-diacetylethylene, the above product is obtained.

I claim:

1. A compound of the formula.

( e a) a wherein M is a polyvalent metal selected from the groupconsisting of antimony, arsenic and tin; -R is a monovalent hydrocarbylradical selected from the group consisting of lower alkyl, monocyclicand bicyclic aromatic, and monocyclic ar(lower alkyl); 11 is the valenceof M; A is a monovalent radical selected from the group consisting ofCN, 000R, C0NH CONHR, CONR COR and N0 and A is a member selected fromthe group consisting of hydrogen and A.

2. The compound 2,2-dibutyl-4-dicyanomethylene-1,3, Z-dithiastannetane.

3. The compound 4-dicyanomethylene-2-phenyl-1,3,2- dithiarsetane.

4. The compound 4-dicyanomethylene-Z,Z-diphenyl-1, 3,2-dithiastannetane.

5. The compound 4-dicyanomethylene-2,2,Z-triphenyl-1,3,2-dithiastibetane.

6. The compound 2,2-dibutyl-4-nitromethylene-1,3,2- dithiastannetane.

References Cited UNITED STATES PATENTS 3,317,573 5/1967 Stamm et a1.260429.7

TOBIAS E. LEVOW, Primary Examiner.

W. F. W. BELLAMY, Assistant Examiner.

US. Cl. X.R.

